CN108456296A - 一种用于服装革的水性聚氨酯树脂及其制备方法 - Google Patents

一种用于服装革的水性聚氨酯树脂及其制备方法 Download PDF

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CN108456296A
CN108456296A CN201711486112.2A CN201711486112A CN108456296A CN 108456296 A CN108456296 A CN 108456296A CN 201711486112 A CN201711486112 A CN 201711486112A CN 108456296 A CN108456296 A CN 108456296A
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polyurethane resin
waterborne polyurethane
diluent
parts
clothing leather
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戴家兵
赵学庭
郑广鹏
冯林林
李维虎
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Hefei Scisky Technology Co Ltd
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Abstract

本发明提供一种用于服装革的水性聚氨酯树脂及其制备方法，该水性聚氨酯包括以下原料组分及重量份：大分子多元醇150～200份；多异氰酸酯30～40份；亲水扩链剂3～5份；催化剂0.1～0.5份；有机硅改性剂0.5～4份；中和剂2～5份；乳化水300～500份；后扩链试剂1～5份。本发明获得的水性聚氨酯树脂，一方面环保无毒，能够满足环保要求；另一方面，所制备的水性聚氨酯用于服装革能完全满足使用性能要求，并且具有相当柔软的手感，同时在水性聚氨酯树脂制备过程中采用一步投料法，可大大降低人力物力成本，提高生产效益。

Description

一种用于服装革的水性聚氨酯树脂及其制备方法
技术领域
本发明涉及高分子聚合物技术领域，具体公开了一种用于服装革的水性聚氨酯树脂及其制备方法。
背景技术
服装革要求手感舒适，较柔软，耐水洗尤其是碱性的水等。服装革除了所用基布和面料层达到要求外，底料也必须达到上述要求。底料偏硬会造成服装革手感差，僵硬。而作为胶粘剂，一方面需要其固化粘结强度高，剥离强度需达到要求，防止服装革在使用中面料脱层。另一方面要求其模量低或者说其分子极性小，这样才可以达到柔软的要求。而低的分子极性与其较高的剥离强度是矛盾的，目前溶剂型聚氨酯胶黏剂可达到较好的效果，但溶剂型服装革在制造过程中使用了大量的有机溶剂DMF，不仅对环境造成了污染，而且制品中残留的溶剂也危害着消费者的健康。水性聚氨酯树脂广泛应用到服装革领域，其不含苯系物、DMF等有机溶剂，具有无毒环保的优点，受到越来越多消费者的喜爱。但现有的水性聚氨酯树脂存在技术上的限制，导致所制成的服装革依旧存在手感硬等的问题。因此，亟需研究出一种新型的水性聚氨酯树脂解决服装革存在的上述问题。
发明内容
本发明的目的在于克服现有的缺陷，提供一种用于服装革的水性聚氨酯树脂及其制备方法，由该水性聚氨酯树脂制备的服装革不仅手感柔软、剥离强度高。
为了实现以上目的，本发明通过包括以下技术方案实现的：
第一方面，本发明提供一种水性聚氨酯树脂，包括以下原料组分及重量份：
优选地，所述大分子多元醇为170～190份。
优选地，所述多异氰酸酯为35～40份。
优选地，所述亲水扩链剂为4～5份。
优选地，所述催化剂为0.3～0.4份。
优选地，所述有机硅改性剂为1～3份。
优选地，所述中和剂为2～4份。
优选地，所述乳化水为350～400份。
优选地，所述后扩链试剂为3～4份。
优选地，所述大分子多元醇选自聚环氧丙烷二醇、蓖麻油、聚异戊二烯二醇、聚异丁烯二醇、聚乙二酸异戊二醇酯二醇、聚四氢呋喃醚中的一种或多种。
优选地，所述多异氰酸酯选自甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、1,5-萘二异氰酸酯(NDI)和二环己基甲烷二异氰酸酯(HMDI)中任意一种或者多种。
优选地，所述亲水扩链剂为2,2-二羟甲基丙酸。
优选地，所述催化剂选自有机铋、有机锌中的一种或两种。
更优选地，所述有机铋为辛酸铋，所述有机锌为辛酸锌。
优选地，所述有机硅改性剂为胺基硅烷偶联剂。
优选地，所述中和剂为三乙胺。
优选地，所述后扩链试剂选自乙二胺、异丁二胺、己二胺、对苯二甲胺、邻苯二甲胺、异氟尔酮二胺和环己二甲胺中的一种或多种。
第二方面，本发明提供一种制备如上述所述的水性聚氨酯树脂的方法，包括以下步骤：
1)按照重量份数将所述大分子多元醇、所述多异氰酸酯、所述亲水扩链剂、所述催化剂和稀释剂加入反应器中混合均匀，然后在60～80℃下反应6～8h；
2)将温度调节至30～40℃，加入所述有机硅改性剂反应0.5～2h；
3)调节温度至50～60℃，再次添加稀释剂并混合均匀；调节温度至0～25℃，加入所述中和剂，中和时间1～5min后，在高速搅拌下加入所述加乳化水使得分散成乳液状态后，然后加入所述后扩链试剂反应0.1～1h；
4)脱除稀释剂，制备获得水性聚氨酯树脂。
优选地，在步骤1)和步骤3)中稀释剂均为丙酮或丁酮。
优选地，步骤1)中稀释剂与所述大分子多元醇的重量比为(5-10)：(150-200)。
优选地，步骤3)中稀释剂与所述大分子多元醇的重量比为(100-150)：(150-200)。
优选地，在步骤4)中所述稀释剂被减压蒸馏脱除。具体操作步骤为：在30～60℃，抽真空-0.07～-0.09MPa的条件下，搅拌或者旋转2～5h，测试结果为无丙酮或丁酮味无臭味，且测试固含量达标即可。
本发明的水性聚氨酯树脂采用大分子多元醇以及多异氰酸酯作为合成的主要原料，其中大分子多元醇提供大分子的软段结构，多异氰酸酯提供大分子的硬段结构；亲水扩链剂提供树脂分子的亲水基团，使得水性结构更稳定；催化剂能够促进反应完全进行，尤其在反应温度低以及多异氰酸酯含量较低的情况下，能够加速反应的完全进行；乳化前加入稀释剂用于降低合成过程中和乳前预聚体的粘度；中和剂能够中和亲水扩链剂中的亲水基团，提高分子链的亲水度；乳化水采用去离子水，用于分散大分子使其成乳液态；后扩链试剂进一步提高树脂的分子量，提高树脂强度和提供硬段。
第三方面，本发明提供一种如上述所述的水性聚氨酯树脂在制备服装革的用途。
综上所述，本发明的一种用于服装革的水性聚氨酯树脂及其制备方法，具有以下有益效果：
本发明获得的水性聚氨酯树脂，一方面环保无毒，能够满足环保要求；另一方面，所制备的水性聚氨酯用于服装革能完全满足使用性能要求，并且具有相当柔软的手感，并且具有优良的剥离强度，同时在水性聚氨酯树脂制备过程中采用一步投料法，可大大降低人力物力成本，提高生产效益。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
表1为实施例1-4中的水性聚氨酯树脂的各原料组分及其配比：
表1水性聚氨酯树脂的各原料组分及其配比
实施例一
1、制备水性聚氨酯树脂
1.1将聚环氧丙烷二醇150g、TDI 35g、DMPA3g、辛酸铋0.4g以及稀释剂丙酮5g，在60℃进行混合反应7h；
1.2调节温度至50℃，加稀释剂丙酮120g并混合；调节温度至需要的乳化温度10℃，添加三乙胺2g进行中和，中和时间2min后在高速搅拌下加乳化水300g，使得分散成乳液状态后添加乙二胺1g进行反应，反应时间1h；
1.3在30℃、抽真空-0.07MPa的条件下进行减压蒸馏，搅拌2h后，测试结果为无丙酮味无臭味，且测试固含量达标，即将稀释剂丙酮脱除，进而获得水性聚氨酯树脂。
2、制备服装革用软底料
将步骤1中制备的水性聚氨酯树脂80g、聚二甲基硅氧烷(有机硅类消泡剂)0.2g、脂肪酸(润湿剂)0.4g进行搅拌混合，再在600r/min的搅拌速度下添加增稠剂聚丙烯酸盐0.5g，使得粘度增大至预定的粘度8000mpa.s，获得服装革用软底料。
3、制备服装革试样
3.1在离型纸上刮涂面料的浆料，再将其烘干固化以获得面料层；
3.2在面料层上刮涂刮步骤2制备的底料；
3.3将基布或者服装革贝斯辊压贴合在面料层的涂有底料的面上，再将其烘干固化获得服装革。
实施例二
1、制备水性聚氨酯树脂
1.1将聚异戊二烯二醇170g和IPDI 30g、DMPA5g、辛酸锌0.1g以及稀释剂丙酮8g，在65℃进行混合反应7h；
1.2将温度调节至10℃，加入胺基硅烷偶联剂KH550 0.5g，混合反应0.5h；
1.3调节温度至55℃，加稀释剂丙酮140g并混合；调节温度至需要的乳化温度15℃，添加三乙胺4g进行中和，中和时间1min后在高速搅拌下加乳化水400g，使得分散成乳液状态后添加己二胺4g进行反应，反应时间0.6h；
1.4在50℃、抽真空-0.08MPa的条件下进行减压蒸馏，搅拌3h后，测试结果为无丙酮味无臭味，且测试固含量达标，即将稀释剂丙酮脱除，进而获得水性聚氨酯树脂。
2、制备服装革用软底料
将步骤1中制备的水性聚氨酯树脂90g、聚氧丙烯氧化乙烯甘油醚(聚醚类消泡剂)0.3g、磷酸酯(润湿剂)0.3g进行搅拌混合，再在800r/min的搅拌速度下添加增稠剂聚丙烯酸盐1g，使得粘度增大至预定的粘度10000mpa.s，获得服装革用软底料。
3、制备服装革试样
3.1在离型纸上刮涂面料的浆料，再将其烘干固化以获得面料层；
3.2在面料层上刮涂步骤2制备的底料；
3.3将基布或者服装革贝斯辊压贴合在面料层的涂有底料的面上，再将其烘干固化获得服装革。
实施例三
1、制备水性聚氨酯树脂
1.1将聚四氢呋喃醚190g和NDI40kg、DMPA4g、辛酸铋0.3g以及稀释剂丁酮10g，混合反应在70℃进行混合反应7h；
1.2将温度调节至50℃，加入胺基硅烷偶联剂Si-602 3g，混合反应2h；
1.3调节温度至60℃，加稀释剂丁酮150g并混合；调节温度至需要的乳化温度25℃，添加三乙胺5g进行中和，中和时间5min后在高速搅拌下加乳化水500g，使得分散成乳液状态后添加邻苯二甲胺5g进行反应，反应时间0.2h；
1.4在60℃、抽真空-0.09MPa的条件下进行减压蒸馏，搅拌4h后，测试结果为无丁酮味无臭味，且测试固含量达标，即将稀释剂丁酮脱除，进而获得水性聚氨酯树脂。
2、制备服装革用软底料
将步骤1中制备的水性聚氨酯树脂100g、聚氧丙烯氧化乙烯甘油醚(聚醚类消泡剂)0.1g、非离子型聚氧乙烯烷基酚醚(润湿剂)0.6g进行搅拌混合，再在1000r/min的搅拌速度下添加增稠剂缔合型聚氨酯2g，使得粘度增大至预定的粘度10000mpa.s，获得服装革用软底料。
3、制备服装革试样
3.1在离型纸上刮涂面料的浆料，再将其烘干固化以获得面料层；
3.2在面料层上刮涂步骤2制备的底料；
3.3将基布或者服装革贝斯辊压贴合在面料层的涂有底料的面上，再将其烘干固化获得服装革。
实施例四
1、制备水性聚氨酯树脂
1.1将蓖麻油200g和HMDI37g、DMPA4g、辛酸锌0.5g以及稀释剂丁酮5g在75℃进行混合反应7h；
1.2将温度调节至80℃，加入胺基硅烷偶联剂Si-602 4g，混合反应1h；
1.3调节温度至50℃，加稀释剂丁酮150g并混合；调节温度至需要的乳化温度10℃，添加三乙胺3g进行中和，中和时间5min后在高速搅拌下加乳化水350g，使得分散成乳液状态后添加环己二甲胺3g进行反应，反应时间0.4h；
1.4在60℃、抽真空-0.09MPa的条件下进行减压蒸馏，搅拌5h后，测试结果为无丁酮味无臭味，且测试固含量达标，即将稀释剂丁酮脱除，进而获得水性聚氨酯树脂。
2、制备服装革用软底料
将步骤1中制备的水性聚氨酯树脂120g、聚氧丙烯氧化乙烯甘油醚(聚醚类消泡剂)0.4g、聚氧乙烯脂肪醇醚(润湿剂)0.5g进行搅拌混合，再在1000r/min的搅拌速度下添加增稠剂缔合型聚氨酯3g，使得粘度增大至预定的粘度12000mpa.s，获得服装革用软底料。
3、制备服装革试样
3.1在离型纸上刮涂面料的浆料，再将其烘干固化以获得面料层；
3.2在面料层上刮涂步骤2制备的底料；
3.3将基布或者服装革贝斯辊压贴合在面料层的涂有底料的面上，再将其烘干固化获得服装革。
测试结果
1、对实施例1-4获得水性聚氨酯树脂的基本特征参数进行性能测试，结果分别如表2所示。
表2水性聚氨酯树脂的基本特征参数测试结果
2、对实施例1-4的水性聚氨酯树脂的物理机械性能进行测试，结果如表3所示。
表3水性聚氨酯树脂的物理机械性能参数测试结果
测试性能 实施例1 实施例2 实施例3 实施例4
100％模量(MPa) 0.52 0.6 0.66 0.48
断裂强度(MPa) 9 10 12 7
断裂伸长率(％) 1200 1400 1400 1300
由表3可知，本发明的水性聚氨酯树脂的100％模量较低，断裂强度以及断裂伸长率均较高，这说明本发明的服装革用软底料不仅具有较好的机械强度，还具有较好的柔软性，保证所制备的服装革手感的柔软性。
3、对实施例1-4所制备的软底料进行应用性能参数的测试，结果如表4所示。
表4实施例1-4所制备的软底料的应用性能参数测试结果
从表4可看出：实施例1～4的软底料在贴合应用中，采用软底料制备的服装革手感柔软，并且剥离力均较大，贴合后的服装革在60℃水洗5min后剥离力损失小于20％，说明软底料的耐水性较好；贴合后的服装革在质量分数为10％的NaOH水溶液浸泡18h后剥离力损失小于20％，说明软底料具有优良的耐碱性；服装革在70℃、90％RH条件下，恒温恒湿放置3周剥离力损失小于30％，说明软底料具有优良的热稳定性。综上所述，由本发明的水性聚氨酯树脂所制得的服装革具有较高的剥离强度、耐热性、耐水性和耐碱性。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

1.一种水性聚氨酯树脂，其特征在于：包括以下原料组分及重量份：
其中，所述有机硅改性剂为胺基硅烷偶联剂。
2.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、1,5-萘二异氰酸酯和二环己基甲烷二异氰酸酯中任意一种或者多种。
3.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述大分子多元醇选自聚环氧丙烷二醇、蓖麻油、聚异戊二烯二醇、聚异丁烯二醇、聚乙二酸异戊二醇酯二醇、聚四氢呋喃醚中的一种或多种。
4.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述催化剂选自有机铋、有机锌中的一种或两种。
5.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述亲水扩链剂为2,2-二羟甲基丙酸。
6.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述中和剂为三乙胺。
7.如权利要求1所述的水性聚氨酯树脂，其特征在于：所述后扩链试剂选自乙二胺、异丁二胺、己二胺、对苯二甲胺、邻苯二甲胺、异氟尔酮二胺和环己二甲胺中的一种或多种。
8.一种制备如权利要求1至7任一所述的水性聚氨酯树脂的方法，其特征在于：包括以下步骤：
1)按照重量份数将所述大分子多元醇、所述多异氰酸酯、所述亲水扩链剂、所述催化剂和稀释剂加入反应器中混合均匀，然后在60～80℃下反应6～8h；
2)将温度调节至30～40℃，加入所述有机硅改性剂反应0.5～2h；
3)调节温度至50～60℃，再次添加稀释剂并混合均匀；调节温度至0～25℃，加入所述中和剂，中和时间1～5min后，在高速搅拌下加入所述加乳化水使得分散成乳液状态后，然后加入所述后扩链试剂反应0.1～1h；
4)脱除稀释剂，制备获得水性聚氨酯树脂。
9.如权利要求7所述的水性聚氨酯树脂的制备方法，其特征在于：在步骤1)和步骤3)中所述稀释剂均为丙酮或丁酮；
和/或，步骤1)中稀释剂与所述大分子多元醇的重量比为(5-10)：(150-200)；
和/或，步骤3)中稀释剂与所述大分子多元醇的重量比为(100-150)：(150-200)。
10.一种如权利要求1至7任一所述的水性聚氨酯树脂在制备服装革的用途。
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Application publication date: 20180828